Exhaust process for the dyeing of synthetic fibre materials

ABSTRACT

Exhaust process for the dyeing of synthetic fibre materials from organic water immiscible solvents with disperse dyestuffs containing carboxamide groups.

United States Patent 1 Neeff et a1. 1

[ EXHAUST PROCESS FOR THE DYEING OF SYNTHETIC FIBRE MATERIALS [75] Inventors: Riitger Neeff, Leverkusen; Dietmar K 2 9 9 n91. b91h 929219 1 7.

[73] Assignee:- Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany 22 Filed: Oct. 16, 1970 21 Appl. No.2 81,548

[30] Foreign Application Priority Data [111 3,792,971 [451 Feb. 19, 1974 [56] References Cited UNITED STATES PATENTS 2,863,714 12/1958 Long et al. 8/173 3,331,829 7/1967 .lirou et al...... 8/174 X 3,510,243 5/1970 Seuret et a1 8/39 3,531,458 9/1970 Ackermann et a1. 8/174 3,622,558 11/1971 Kolliker 8/50 X FOREIGN PATENTS OR APPLICATIONS 1,048,878 11/1966 Great Britain 8/174 Primary ExaminerLe0n D. Rosdol Assistant Examiner-T. J. Herbert, Jr.

[5 7 ABSTRACT Exhaust process for the dyeing of synthetic fibre materials from organic water immiscible solvents with disperse dyestuffs containing carboxamide groups.

26 Claims, No Drawings carbon tetrachloride, 1,1-dichloroethane, 1,2- dichloroethane, 1,1,2-trichloroethane, 1,1,1,2- tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, l-chloropropane, 2-chloropropane, 1,2- dichloropropane, l-chlorobutane, 2-chlorobutane, 1,4- dichlorobutane, l-chloro-2-methylpropane or 2-chloro-2-methylpropane, as well as aliphatic fluorinated and fluorochlorinated hydrocarbons, such as perfluoro-n-hexane, l,2,2-trifluoro-trichloroethane and trifluoro-pentachloropropane; aromatic chlorinated and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene, 1,1,1- trichloroethane and l,l,l-trichloropropane have proved particularly satisfactory. Mixtures of these solvents may also be used.

The carboxamide group-containing disperse dyestuffs to be used according to the invention may be based on any type of dyestuff provided they contain at least one carboxamide group. The dyestuffs to be used according to the present process may belong, for example, to the series of metal-containing or metal-free monoor polyazo dyestuffs or (azo) methine dyestuffs; to the series of anthraquinone dyestuffs and condensation products of the latter which contain more than three anellated rings; other suitable dyestuffs are oxazine, nitro-diphenylamine, naphthalic acid diand triphenylmethane dyestuffs, naphtholactam condensation dyestuffs, quinophthalone dyestuffs, and dyestuffs derived from naphthoquinone and naphthoquinonimine, as well as other condensation dyestuffs. ln addition to the carboxamide groups required by definition, the dyestuffs may contain other conventional substituents, such as halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy, nitro, sulphone groups, optionally substituted sulphonamide groups; optionally substituted or acylated amino groups; alkylthio and arylthio, hydroxy, hy-

droxy-alkyloxy, amino-alkyloxy, cyano, cyanoalkyl radicals as well as alkyl, aryl, aralkyl radicals substituted in a different way, and the like.

The dyestuffs contain one or more carboxamide groups which are linked to aromatic nuclei of the basic ring system of the dyestuff itself or to aryl, aralkyl or aliphatic groupings standing in an external position. The number of carboxamide groups preferably amounts to 1 to 4.

The carboxamide groups are characterised by the formula in which the radicals B and 8,, independently of one another, denote hydrogen or optionally substituted lower alkyl or alkenyl groups, aryl radicals or heteroaryl radicals. The radicals B and B, together may also form a ring which may be interrupted by hetero atoms.

Examples of radicals B and B, are the methyl, ethyl or trifluoro-methyl radicals; the B-hydroxy, B-chloro, B-bromo, B-methoxy, B-methylthio, B-methylsulphonyl or B-cyanoethyl groups or an ethylene, B-chloroor B-bromo-ethylene radical. If B and B, stand for an aryl radical, this is preferably a phenyl radical which may be substituted by one or more halogen atoms, such as fluorine, chlorine or bromine, nitro groups, trifluoromethyl, hydroxy or lower alkoxy radicals, carboxyl or carboxamide groups, acylamino groups, sulphonamide or lower alkylsulphonyl radicals. Suitable heteroaryl radicals are, for example, the pyridyl, pyrrolyl, pyrimidinyl, furanyl, thienyl or sulpholanyl radicals. Examples of rings formed by B and B, and possibly interrupted by hetero atoms are the pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl or thiomorpholinyl dioxide rings.

Numerous dyestuffs containing carboxamide groups are known; they are prepared in the usual way by converting appropriate dyestuff intermediates which carry one or more carboxamide groups linked to the nucleus or in external position, into the desired final products while retaining the carboxamide groups and, if desired, carrying out further conversion reactions. Obviously, it

is also possible to start from dyestuffs containing one or more carboxyl groups and to convert the carboxyl groups into the corresponding amides in the usual way via reactive intermediary stages, such as e.g. the esters or acid chlorides. In the case of azo dyestuffs, the usual conversion reactions are diazotisation and coupling as well as condensation; for most other dyestuff classes they are condensation reactions.

Examples of suitable azo dyestuffs containing car- 0 boxamide groups are the compounds given below where the radical f h i u 0) 0) F) m 0) W I '14 gz x -..--x x x n 1 3 HZN 0 NH; mN 0 NH; (5 NH: with dicarboxylic acids of the general formula: g; g NH: HQN 0 OH HOOC-X-CO -N II I B] 2 X=a1kylene, arylene, bivalent heteroeyclie radical or I l8 a compound of the formula B ll CO-N 5 no 0 NH: clogs K B,

-0-Cr-Ce-alkylenoC0-N furthermore, the unthraquinone dyestufi assembled in the following table: B

SCz-Cs-aikylene-CON 0') o x x x n a NHC --C2-alky1ene-C0N I I 0 I I B 0 X C0-N O OH X X X X II B CON | Bi 0 X a 0 NH, x x x x x x x 3 l I A 0-0|- Cralkylen-C O-N\ p on x x x x l X C? C|CralkyleneC0N 0 4m NE Q B 0 0H ll SC1C:-a1kylono-C0N so B: u K x g x X 0 Anthraquinone condensation products which contain carboxamide groups and carry more than three am]- 0 NH2 lated rings are the following, for example. lsothlazole- H0 (I) OH X X X X X X X anthrgngs, Ns N-S 00 N H OsN 0 v 1 (NH) [alkyl (NH!) aryl CO-NH 0 on: on x x x x x x x B 1 1 l2 Pyrazole-anthrones, such as Anthraquinone dyestuffs of the above formulae are prepared according to the principles of synthesis lr known in anthraquinone chemistry. For this purpose,

I H l B condensation reactions with suitable starting comcN 5 pounds are primarily suitable. For example, amino I l i 131 group-containing anthraquinone compounds in which the amino groups stand either in an external position I 1 or, preferably, in a position linked to the nucleus, can B be condensed with suitable carboxyaryl-acid halides or I0 anhydrides, e.g. carboxyphenylor carboxynaphthyl- X=S'a1kyC0 N\ NH'a1kyl'C0 N\ sulphonic acid or carboxylic acid chlorides or bro- B1 B1 mides, to form the corresponding acid amides; or anthraquinone compounds containing mobile halogen S-aryl-CO-N NH-aryl-CO-N atoms, for example, can be reacted with carboxyarylamines, such as carboxyphenylor carboxynaphthylamines, to form the corres ondin carbox ar laminoand also dyestuffs of the type anthraquinone derivatives and the m; Zarboxyl groups still present in the resultant dyestuffs can be converted in known manner into carboxamide groups. Alternatively, anthraquinone compounds containing N amino groups, for example, can be condensed with car- I J boxamidoaryl acid halides or anhydrides or e.g. anthra- =0 quinone compounds with mobile halogen atoms can be I HN I condensed with carboxamido-arylamines.

0:0 Anthraquinone ether and thioether derivatives in which carboxamide groups are contained in alkyl, aral- I kyl or aryl radicals of the ether or thioether component can be prepared according to similar principles of synthesis. Another possibility of synthetising carboxamide X 0 X group-containing anthraquinone dyestuffs to be used B B according to the invention consists in that anthraquinone-acid halides, such as carboxylic acid and sul- X=S--alky1CO-N NHalkylOON phonic acid chlorides or bromides, are converted mto B1 B1 the corresponding amides or esters with the aid of suitable amino or hydroxy compounds which also contain y y at least one carboxamide group. Of course, it is also 13 B1 possible to use those anthraquinone compounds for the B present process, in which one or more carboxamide groups are linked to the nucleus or which contain car- O 40 boxamide groups linked to the nucleus as well as in an B l B 0 l external position.

Representatives of nitro dyestufis containing carbox- Bl I 3 amide groups are, for example, dyestuffs of the following formula:

It has frequently proved advantageous for the dyebaths to contain small amounts, i.e., up to 1 per cent by weight, preferably 0.5 per cent by weight, of water, referred to the weight of the organic solvents.

Furthermore, the addition of non-ionic auxiliaries to the dyebaths has proved useful in some cases. Suitable non-ionic auxiliaries are primarily the known interfaceactive ethoxylation and propoxylation products of fatty alcohols, alkylphenols, fatty acid amides and fatty acids, as well as mixtures thereof; the auxiliaries are used in an amount of 0.05-2 per cent by weight, referred to the weight of the organic solvents. Instead of immediately adding the auxiliaries to the dyebaths, they can advantageously be used for pasting the dyestuffs containing carboxamide groups and thus be added to the dyebaths in the form of a dyestuff/auxiliary paste.

The synthetic fibre materials to be dyed according to the invention are primarily fibre materials of polyesters, such as polyethylene terephthalate, polycyclohexane-dimethylene teraphthalate; heterogeneous polyesters obtained from terephthalic acid, sulphoisophthalic acid and ethylene glycol; or copolyether ester fibres obtained from p-hydroxy-benzoic acid, terephthalic acid and ethylene glycol; cellulose triacetate, cellulose Zia-acetate, polyacrylo-nitrile, synthetic polyamides such as hexamethylene-diamine adipate, poly-ecaprolactam, or m-amino-undecanic acid and polyurethanes. The fibre materials may be present in various stages of processing, e.g. as filaments, flocks, combed material, yarn, or as piece goods such as fabrics or knitted fabrics or as ready-made goods.

Dyeing according to the invention is preferably carried out in closed apparatus, for example, by introducing the fibre materials in a goods to liquor ratio of 1:3 to 1:30 into the dispersions of the disperse dyestuffs in the organic water-immiscible solvents at room temperature, heating the dyebath to 60l 70 C and maintaining this temperature until the bath is exhausted; in general, this will be the case after -60 minutes. After cooling to room temperature, the liquor is removed and, possibly after briefly rinsing with fresh organic solvent, the fibre materials are freed from the adhering solvent by filtering off with suction or centrifuging and subsequent drying in a warm current of air. With the aid of the process according to theinvention it is possible to dye synthetic fibre materials from organic solvents in a simple way, high dyestuff yields and excellent fastness properties being achieved.

The dyestuffs are applied in an amount of 0,01 to 3 percent by weight referred to the weight of the fibre materials.

The carboxamide group-containing dyestuffs to be used according to the invention are largely insoluble in organic water-immiscible solvents. They are superior to the dyestuffs hitherto-used for'dyeing synthetic fibre materials from organic solvents on account of a substantially higher affinity and an increased fastness to sublimation. Another advantage of the process according to the invention consists in that the depth of colour of the resultant dyeings at a given ratio dyestuff: dyeing material is substantially independent of the concentration of the dyestuff in the dye-bath and therefore also independent of the liquor ratio. Due to this independence of the liquor ratio, the process according to the invention can be used in all known dyeing devices, such as'winches, jiggers, etc. which, as isknown, are operated with different liquor ratios, and it yields reproducible dyeings.

It should be pointed out that mixtures of the dyestuffs to be used according to the invention sometimes give a better dyestuff yield than the individual dyestuffs.

. The parts given in the following Examples are parts by weight.

EXAMPLE 1 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from 1 part of the monoazo dyestuff 4-aminobenzoic acid ethyl ester 1-phenyl-5-pyrazolone-3-carboxylic acid amide and 1,000 parts tetrachloroethylene.

The bath is heated to C within 10 minutes with .vivid circulation of the liquid, and the same temperature is maintained for 30 minutes. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40 C for 5 minutes. After separating the rinsing liquor, the dyed material is centrifuged and dried in an air current. A strong yellow dyeing of excellent fastness to sublimation and very good fastness to washing and light is obtained.

An equally good yellow dyeing was obtained in the same way on a fabric of polycyclohexane-dimethylene terephthalate fibres.

Yellow dyeings of equally good fastness properties were obtained when the dyestuff mentioned above was replaced with the same amount of one of the following monoazo dyestuffs:

EXAMPLE 11 100 Parts of a fabric of triacetate fibres are introduced at room temperature into a dyebath prepared from 1 part of the monoazo dyestuff 4-aminobenzoic acidmethyl ester l-phenyl-5-pyrazolone-3- carboxylic acid piperidide and 1,000 parts tetrachloroethylene.

The bath is heated to 1 10 C within 20 minutes with vivid circulation of the liquor, and the same temperature is maintained for 45 minutes. The liquor is then separated and the fabric rinsed with fresh trichloroeth- EXAMPLE l3 ylene at sgparaung the rms.mg liquor the 100 Parts of polyacrylonitrile fibres are dyed in a dyed i is fred f h adhermg Solvent g bath prepared as described in Example 3. The bath is centrifuging and drying in an air current. A full, brilheated to C within 20 minutes, and the Same liant yeuow dyeing of excellent fastness propemes 5 perature is maintained for 30 minutes. After the usual Obtamed' washing and drying, a yellow dyeing of good fastness EXAMPLE 2 properties is obtained.

100 Parts of yarn of acetate filaments are introduced EXAMPLE 14 at about 22 C into a dyebath prepared from 10 1 part of the monoazo dyestuff 4-ami be O C acid 100 Parts of a fabric of polyethylene tercphthalate fipyrrolidide l-phenyl-5-pyrazolone-3- bres are heated in a dyebath containing carboxylic acid methylamide 1 part of the monoazo dyestuff 3-aminobenzoie acid 1,000 parts tetrachloroethylene amide l-methyl-2,4-dihydroxy-quinoline in 1.5 parts oleic acid ethanolamide 15 1,000 parts tetrachloroethylene 1.5 parts oleyl alcohol eicosaethylene glycol ether to 1 15 C within minutes, and dyed at the said temand perature for 30 minutes. After separating the liquor, 6 parts of water. rinsing and drying, there is obtained a brilliant greenish The bath is heated to 78 C within 20 minutes, and the yellow dyeing of very good fastness to sublimation, same temperature is maintained for 45 minutes. After 20 washing and light.

separating the dyeing liquor and rinsing with fresh tet- Dyestuffs of equally good fastness properties in the rachloroethylene, the dyed material is freed from the shades indicated in the following Table were obtained adhering solvent by filtering off with suction and drying when the above dyestuff was replaced with the same in an air current. A brilliant yellow dyeing is obtained. amount of one of the dyestuffs mentioned in the Table:

Example Diazo component Coupling component Shade Z-amino-t-nitrol-methyl-2,4- greenish benzoic acid amide dihydroxyquinoline yellow 16 4-amino-benzoie acid Bcyanoethyl-amide l7 S-amino-benzoic acidanilide l8 3-amin0-benzoic acidbis-(p-eyanoethyU- amide l9 3-amino-benzoic acid fl-cyanoethyl fi-hydroxyethyl amide 3-amino-benzoic acid (3-chloroanilide) 2| 3-amino-benzoic acid (4-methoxyanilide) 22 4-amino-3-nitro-benzoic acid-phenyl-methylamide 23 4-amino-3-nitrebenzoic acid-pyridide 24 3-amino-4-nitro-benzoic acid-(3-sulpholanylamide) 25 2-amino-3,5-dinitro-benzoic 3-methyI-N,N- reddish acid-[3-methoxyethyl-amide dihydroxyethylblue aniline 26 3-amino-4-ehlore- 3-methyl-N.N- reddish benzoic aciddihydroxyethylorange (l-naphlhylamide) aniline 27 S-nitro-aniline N,N-bis-(methylaminoreddish carbonylmethyl)- yellow 28 2-ehloro-4-nitro- N,N-dihydroxyethylred aniline aniline-bis-(maleie acid amide semiester 29 S-amino-l ,2,4-tri- N,N-bis-(fi-cyanoyellow azole-S-carboxylic ethyU-aniline acid amide 30 2-cyano-4-nitro- 2-ethoxy-5-aeetaminonavy aniline N,N-bis-(methylaminoblue earbonylethyl)-aniline 3| 2,4-dinitro-6-bromo- Z-ethoxy-S-aeetaminogreenish aniline N,N-bis-(dimethylblue aminocarbonylelhyhaniline 32 2-cyano-4-nilro- N,N-bis-(B-amino redaniline carbonyle'tliyfi ahiline 33 2,4-dinitro-aniline N,N-bis-(fl-methylredaminoearbonylethyhbrown aniline 34 2-amino-4-nitro- 3-aeetylamino-N,N- violet benluic ueiddiethylaniline (2,5-dichlnro-anilide) 35 2-eyuno-4-nilrn- 4-methoxy-3-(N,N-hishlue aniline v fl-hydroxyethy|umino)- unilido-glururie acid elhylnmide 36 2-eyuno-4-nilru- N,N-his-(fi-hydroxybluish aniline elhyl-gluturic acid red semiester amide) Example Diazo component Coupling component Shade 37 2-ch10ro-4-nitro- 3-methyl-ani1ine-N,N- red aniline bis-(3,3-propionic acid amide) 38 2,6-dichloro-4- Aniline-N,N-bis-(3,3- brown nitro-aniline propionic acid amide) orange 39 2-ch1oro-5-trifluoro- Ani1ine-N,N-bis-(3.3- orange methyl-aniline propionic acid morpholide) 4O 2,S-dich1oroaniline 3-methy1-ani1ine-N,N- red bis(3,3-propionic acid amide) 41 2-ehlor0-4-nitro- N-cthyl-aniline-N-(3 red aniline propionic acid-3- carboxyanilidc) 42 4-nitr0-2-amino- N-(fi-cyanocthyU- red venzoic acid amide aniline-N-(3-propionic acid) 43 2-amino-4nitro- N-(B-hydroxyethyhred phenoxy acetic acid N-(B-cyanoethylJ- bis-(B-hydroxyaniline cthyl)-amide 44 2-chloro-4-nitro- Anilinc-N-(3-propionic red aniline acid-3-ethoxyanilide) 45 2-cyan0-4-nitro- Aniline-N-(B-hydroxyviolet aniline ethyl-phthalic acid semicster amide) 46 2-chloro-4-nitro- N-methyl-aniline-N- red aniline (B-hydroxyethylglutaric acid semicster amide) 47 2-chloro-4-nitro- N-methyl-aniline-N- red aniline (fl-hydroxyethyl-suecinie acid semiester-methylamide) 48 2-cyano-4-nitr0 2-cthoxy-5-acetylaminoblue aniline N,N-bis-(B-hydroxyethyl-glutaric acid semiester amide) 49 2,4-dinitro6bromo- 2-ethoxy-5-acetylaminoblue aniline N,N-bis(fl-hydroxyethyl-glutaric acid semiestcr amide) 50 3-phenyl-5-amino- 3-N,N dimethylaminoredthiadiazole-( 1,2,4) anilido-glutaric acid brown methylamide EXAMPLE 51 EXAMPLE 58 100 Parts of a knitted fabric of polyethylene terephthalate fibres are dyed in a dyebath containing 1 part of the disazo dyestuff 3-amin0benzqic acid methylamide 1-amino-2,5-dimeth0xybenzene salicylic acid amide in 2,000 parts tetrachloroethylene at 115 C for 30 minutes. After the usual rinsing and drying, a brown dyeing of very good fastness to sublimation, washing and light is obtained.

Dyeings of equally good fastness properties were obtained when the above dyestuff was replaced with the same amount of one of the followingdisazo dyestuffs:

Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from 0.5 parts 4-(3-aminocarbony1-phenylamino)-5-nitrol ,8-dihydroxy-anthraquinone 0.5 parts 4-(3-aminocarbonyl-phenylamino)-8-nitrol ,5 -dihydroxy-anthraquinone 1.5 parts oleic acid ethanolamide 1.5 parts oleyl alcohol eicosaethylene glycol ether 6 parts of water and 500 parts tetrachloroethylene.

The bath is heated to 120" C within 10 minutes with vivid circulation of the liquor, and the same temperature is maintained for 45 minutes. After separating the dyeing liquor, the dyed material is rinsed with fresh solvent at 40 C, the rinsing liquor is removed and the material dried in an air current. A deep blue dyeing of excellent fastness to light and sublimation is obtained.

Equally satisfactory blue dyeings are obtained when the 500 parts tetrachloroethylene are replaced with the same amount of 1,1,2-trichloroethane, 1,1,1 ,2-

"tetrachloroethane, l,1,2,2-tetrachloroethane, pentasalicylic acid amide chloroethane, 1,2-dich1oropropane, 2-chlorobutane, 1,4-dichlorobutane, perfluoro-n-hexane, l,2,2-tri fluoro-triehloroethane, trifluoro-penta-chloropropane, chlorobenzene, fluorobenzenc, chlorotoluene or benzotrifluoride.

EXAMPLE 59 100 Parts of fibre yarn of poly-e-caprolactam are introduced at room temperature into a dyebath contain- 1 part of the dyestuff mixture mentioned in Example 1,000 parts tetrachloroethylene. The bath is heated to 100 C within 20 minutes with vivid circulation of the liquor, and the same temperature is maintained for 40 minutes. After this period of time, the liquor is separated, the material briefly rinsed with fresh solvent and, after centrifuging, the dyeing is dried in an air current. A brilliant blue dyeing of good fastness properties is obtained.

An equally good dyeing was obtained on yarns of polyhexamethylene-diamine adipate fibres.

The strength of colour of the dyeing can be increased by percent by adding 1 part oleyl ethanolamide 1 part oleyl alcohol eicosaethylene glycol ether and 4 parts of water I to the dyebath.

EXAMPLE 60 100 Parts of a polyethylene terephthalate fabric are dyed at 115 C for 30 minutes in a dyebath consisting of 1 part 4-(3-aminocarbonyl-phenylamino)-8-amino- 1,5-dihydroxy-anthraquinone,

3 parts oleic acid ethanolamide 3 parts oleyl alcohol eicosaethylene glycol ether 12 parts of water and 1,600 parts tetrachloroethylene. After rinsing with fresh tetrachloroethylene and drying, there is obtained a strong blue dyeing of very good fastness to sublimation, washing and light.

Dyeings of equally good fastness properties in the shades indicated in the following Table were obtained when the above dyestuff was replaced with the same amount of one of the dyestuffs mentioned in the Table:

75 1-hydroxy-4-(3-aminocarbonylphenylamino)-anthraquinone imino-4,7-diamino-5,6-phthaloylisoindoline Example Dyestuff Shade 76 1-amino-4-(3-aminocarbonylpheny1 blue amino)-anthraquin0ne 77 1-amino-4-(4-aminocarbonylphenylthio)- red anthraquinone 78 1,5-diamino-2-(3-methylaminocarbony1- greenish blue 4-hydroxy-phenyl)-4,8-dihydroxyanthraiminone 79 1,S-diamino-3-(3-methylaminocarbonylblue 4-hydroxy-phenyl)-4,8 dihydroxyanthraquinone 80 l,;dihygroxy mgg methylanigreddish blue carfimylethylaminoy8-nitroanthraguinone 81 l,5-dihydroxy-4-(B-aminocarbonylblue ethylamin0)-8-amino-anthraquinone 82 1,8-dihydroxy-4-(B-aminocarbonylblue ethylamino)-5-amino-anthraquinone 83 1,S-dihydroxy-4,8-di-(,B-methylaminogreenish blue carbonylethylamino)-anthraquinone 84 l,8-dihydroxy-4,S-di-(B-aminocarbonylgreenish blue ethylamino)-anthraquinone 85 1,4,5,8-tetra-(l3-ethylaminocarbonylblue-green ethylaminol-anthraquinone 86 1,5-diamino-2- or -3-(aminocarbonyl)- blue methylthio)-4,8-dihydroxyanthraquinone 87 l-amino-2-(aminocarbonylmethoxy yellowish red methyl-1,4-cyclohexylmethoxy)-4- hydroxy-anthraquinone 88 1-amino-2-(y-(fi-hydroxyethylaminoyellowish red carbonylmethoxy)-propoxy)-4- hydroxy-anthraquinone 89 1,4-dihydroxy-2-(4-B-hydroxyethylscarlet aminocarbonylphenylthiolanthraquinone 90 1,4-dihydroxy-2-(B-aminocarbonylethylscarlet thio)-anthraquinone 91 1-amino-2-(,Baminocarbonylethylthio)- blue 4-cyclohexylamino-anthraquinone 92 1,9-is0thiazole-anthrone-2-carboxylic yellow acid (B-carboxyanilide) 93 1 ,9-isothiazole-anthrone-2-carboxylic yellow acid (4-acetylaminoanilide) 94 5-(2-(bis-B-hydroxyethylaminocaryellow bonyl)-ethylamino)- l ,9-is0thiazoleanthrone 95 S-(Z-aminocarbonylethylthioJ-1,9- yellow isothiazole-anthrone 96 5-(2-aminocarbonylethylamino) l ,9- greenish pyrazole-anthrone yellow 97 4-(3-aminocarbonylphenylaminoJ-N- red methyl-1,9-anthrapyridone 98 2-(2-diethylaminocarbony1ethylamino)- blue 3,4-phthaloylacridone 99 Naphthoylenbenzimidazole-Bz-3- yellow carboxylic acid amide 100 Naphthoylenbenzimidazole-1,8-diyellow (carboxylic acid-methylamide) 101 1,4-diamino anthraquinone-2-sulphonic blue acid-(4-aminocarbonyl-phenylester) 102 1-amino-2-(B-aminocarbonyl-methoxyyellowish red ethoxy)-4-hydroxy-anthraquinone 103 1,8-dihydroxy-4-(3-methylaminogreenish blue' carbonyl-methoxyphenylamino)-8- nitro-anthraquinone 104 l,4,5-tri-(B-ethylaminocarbonyl-ethylgreenish blue aminol-8-hydroxy-anthraquinone 10S l-amino-2-(4-B-hydroxyethylaminobluish red carbonyl-phenoxy)-4-methylsulphonylamino-anthraquinone 106 1-amino-2-(B-methoxyeth0xy)-4-(3- bluish red aminocarbonyl-phenylsulphonylamino)-anthraquinone 107 1,5-dihydroxy-2-or-3-bromo-4,8-di-(B- blue aminocarbonylethylaminol-anthraquinone 108 1,8-dihydroxy-2- or 3-bromo-4,5-di-(B- blue aminocarbonylethylaminoj-anthraquinone 109 1,5,8-trihydroxy-4-(3-aminocarbonylblue red phenylamino)-anthraquinone l 10 1-0xo-2-(B-aminocarbonylethyl)-3- turquoise EXAMPLE 111 100 Parts polyethylene terephthalate filaments are heated in a dyebath consisting of 1,600 parts tetrachloroethylene at 115 C for 30 minutes with vivid circulation of the liquor, then centrifuged and rinsed with tetrachloroethylene at 40 C for 5 minutes. A strong greenish yellow dyeing of very good fastness to sublimation, washl ing and light is obtained.

An equally satisfactory dyeing is obtained when the tetrachloroethylene is replaced with the same amount a of 1,1,2-trichloroethane.

Similar dyeings are also obtained when fibres of anion-modified polyethylene terephthalate (Dacron 64) or anion-modified polyhexamethylene-diamine adipate (Nylon T 844) are dyed, instead of polyethylene terephthalate fibres.

Dyeing of equally satisfactory fastness properties in the shades indicated in the following Table were obtained when the above dyestuff was replaced with the same amount of one of the dyestuffs mentioned in the Table:

Example Dyestuft" shade 112 4-(4-aminocarbonylphcnylamino)-3-nitroyellow benzene-sulphonic acid anilide 113 4-(4-aminocarbonylphenylamino)-3-nitroyellow benzo-sulphonie acid-(4-aminoearbonyl-phenylamide) l 14 4-(2,5-dichlorophenylamino)-3-nitro-bengreenish zene-sulphonie acid-THhiMfi-hydroxyethylJ- aminoearhonylphenylamide) yellow 115 4-(3-methoxyphenylaniino)-3-nitro-benreddish zene-sulphonie acid-(Z-aminoearhonylphenyl-amidc) yellow 1 16 4-(3-carhoxyphenylaminoJ-3-nitro-benyellow zene-sulphonic acid -(4melhylaminocarbonyl-phenylamide) l 17 4-(3-fluorophenylamino)-3-nitro-benzcneacid-(4-aminocarbonyl-3-hydroxy-phcnylamide) greenish yellow 1 18 4-(4-cyanophenylamino)-3-nitro-benzcneyellow sulphonic acid-(4-aminocarbonylphenyl-amide) 1 19 4-(3-cyan0phenylaminol-S-nitro-benzene yellow sulphonic acid-(4-[3-eyanoethylaminocarbonylphenylamide) 120 4-(2-nitrophenylamino)-3-nitro-benzeneyellow sulphonic acid-(4-aminocarbonylmethox hen a HEAVY yellow 121 4-(4-mcthylphenylamino)-3-nitro-benzcneyellow sulphonic acid-(4-aminocarbonylphenyl-amide) 122 4-(3-trifluoromethylphenylamino)3-nitrogreenish benzene-sulphonic acid-(4-B-aminocarbonylethoxyphenylamide) y 12 3 4-(3-aminocarbonylphenylamino)-3-nitroyellow benzene-sulphonic acid-(4-aminosulphonyl-phenylamide) 124 4-(4earboxymethoxyphenylamino)-3-nitroreddish benzene-sulphonic acid-(4-aminocarbonyl-phenylamide) yellow 125 4(4-[3-carboxyethoxyphenylamino)-3-nitroreddish benzene-sulphonic acid-(3-aminocarbonyl-phenylamide) yellow 126 4-phenylamino-3-nitro-benzene-sulphonic yellow 65 acid(4-aminoearbonyl-phenylester) 127 4-(4-aminoearbonylphenylamino)-3-nitroyellow benzenesulphonic acid-(4aminocarbonylphenylester) 128 4-(4-aminoearbonylphenylamino)-3-nitroyellow benzene-sulphonic acid-(4-bis-( B-hydroxy-ethyl) -aminocarbonyl-phenylcstcr) -Continued Example Dyestuff Shade 129 4-phenylamino-3-nitro-benzoic reddish acid-(4-aminocarbonyl-phenylamide) yellow 130 4(4-aminocarbonyl-phenylamino)-3-nitroreddish benzoic acid-(4-aminocarbonyl-phenyl-amide) yellow 131 4'(4-arnin0carbonyl-phcnylamino)-3-nitroreddish benzoic aeid-phenylamide yellow 132 4-(4-methylphenylamino)-3-nitro-benzoic acid-(3-bis-(B-hydroxyethyl)-amino-phenylamide) reddish yellow 133 4-( 3-clh0xyphenylamino)-3 nitro benzoic reddish acid phenylamide yellow 134 4-(2-cyanophenylamino )-3-nitro-benzoic reddish acid-(3-morpholinylcarbonyl-phenylamide) yellow 135 4-pheylamino-3-nitro-benzoic aeid-(3,S-bis-(aminocarhonyl)-phenylamide) reddish yellow 136 4-(4-nitrophenylamino)-3-nitro-benzoie acid-(3-methylaminoearbonyl-4-hydroxy-phenylamide) reddish yellow 137 4-(3.4-dieh1orophenylamino)-3-nitro benzoic acid-(4-B-cyanoethylamino-carbonylphenylamide) yellow 138 4-( 3-methylaminocarbonyl-phenylamino)- 3-nitro-benzoic aeid-(4-arninocarbonyl-phe nylamide).

reddish yellow 139 4-phenylamino-3-nitro-benzoic acid (4-aminocarbonyl-phenylester). yellow 140 4-(4-aminoearbonyl-phenylamino)-3-nitroyellow benzoic acid phenylester 141 4-(4-aminocarbonyl-phenylamino)-3nilroyellow benzoie aeid-(4-aminocarbonyl-phenyl-cster) 4-(4aminocarhonyl-phenylamino)-3-nitroyellow benzoic acid amide 143 4-phenylamino-3-nitro-benzoic yellow acid-bis-(fl-hydroxyethyl)-amide 144 4-(2-nitrophenylamino)-3-nitro bcnzoic acid-bis-(B-cyanocthyl)-amide yellow 145 4-(2-methylsulphonyl-4-nitroyellow phenylamino)-3-nitro-benzoic acid amide 146 4-(4-nitro-2-cyanophenylamino)-benzoic yellow acid amide 147 4-(4-carboyxphenylamino)-3-nitro-benzoic yellow acid amide I48 4-(4-aminocarbonyl-phenylamino)-3-nitroyellow benzoic acid amide 149 4-(4-an1inocarbonylphenylamino)-3-nitroyellow benzoic acid-bis-(B-hydroxyethyl)-amide 150 4-(4-aminocarbonylphenylamino )-3-nitroyellow benzencsulphonie acidbis-(B-hydroxy-ethyl)amlde 151 4-(4-aminocarbonyl-phenylamino)-3-nitro yellow benzene sulphonic acid amide 100 Parts of yarn of polyethylene terephthalate fibre 55 are dyed in a dyebath consisting of 1 part of the quinophthalone dyestuff of the formula EXAMPLE 152 2.5 parts oleic acid ethanolamide 2.5 parts oleyl alcohol 10 parts of water and 23 sublimation, washing and light.

An equally satisfactory dyeing is obtained when the above quinophthalone-carboxamide dyestuff is replaced with a bromination product which contains about 1 atom bromine per molecule and is obtained in 5 known manner by bromination in nitrobenzene or glacial acetic acid.

Clear yellow dyeings are also obtained when the dyestuff mentioned in Example 152 is replaced with equal amounts of the quinophthalone-carboxylic acid amides 19 indicated in the following Table:

in- 0H 00 B i H CON Ra C0 B1 R2 B: B1

II II NHCH: H II N(CH:): 11 II 11-43 I: It It NHCHr-CH2OH H II N(CI{2-CH20I1)2 II 11 NHCIIzCHz-CN 100 Dr n 11 "'Nm J M l 161. C1 01 II NHCH; 162 02 11 I1 N112 m3. 01110 II 11 N1I---(1HeCH2-OII 1m Gm-CoNIl 11 ll NtCIla): 165 11 II on; Nlh 166 11 n C1130 N111 Greenish yellow dyeings are obtained when the quino-phthalone-carboxamide dyestuff mentioned in Example 152 is replaced with equal parts of one of the methine dyestuffs of the formulae 10 CH; CH; I I CN =cH-cr1=c-coNH,

CH3 ooNH,

cmo 0 CQCO o-cm- We claim: 1. Process for dyeing synthetic fiber material by exhaustion comprising introducing synthetic fiber material into a dyebath which is a dispersion consisting essentially of A. organic solvent; and B. disperse dyestuff containing 1 to 4 carboxamide groups and largely insoluble in said dyebath; said organic solvent consisting of tetrachloro-ethylene, trichloroethylene, 1,1,1-trichloro-ethane, 1,1,1- trichloropropane or mixtures thereof; and dyeing at a temperature of 60 to C for 10-60 minutes until the dyebath is exhausted. 2. The process of claim 1 in which said organic solvent consists of tetrachloroethylene.

3. Process according to claim 1, wherein said carboxamide group-containing disperse dyestuff is a monoazo dyestuff of the formula in which R stands for a C -C -alkyl radical which may be substituted by a cyano or carboxamide group, an aryl radical which may be substituted by a carboxamide group or a sulpholanyl radical; R denotes a C,-C -alkyl, C -C -carbalkoxy or a carboxamide group; R denotes a halogen atom, a carboxyl, C,

C carbalkoxy or a carboxamide group; and R means a hydrogen atom or a nitro group, with the proviso that at least one of the radicals R R or R is a carboxamide group or a radical containing a carboxamide group. 4. Process according to claim 1, wherein said monoazo dyestuffs of the formula in which R denotes a carboxamide group and R means a hydrogen atom or a nitro group.

5. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a monoazo dyestuff of the formula in which R and R independently of one another, stand for tc rQ-a k l s wnetfltfbs grev a in which R, and R independently of one another, denote hydrogen or a C,-C.,-alkyl group or the grouping -CH -CH -CONRR" in which R means hydrogen, a C,-C.,alkyl or an optionally substituted aryl radical, and R means hydrogen or a C,C.,-alkyl radical; R means hydrogen, a halogen atom, a nitro, cyano or carboxamido-methyl-oxy group; R denotes hydrogen, a halogen atom or a nitro group;

'R,, is hydrogen, a C,-C.,-alkyl or C,-C.,-alkoxy group;

and R means hydrogen, an acetylamino or 'y-carbamoylbutyrylamino group, with the proviso that at least one of the radicals R,, R R R or R is a carboxamide group or a radical containing a carboxamide group. 6. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a disazo dyestuff of the formula s t a in which a B2 Ra in which X stands for a group -SO or -CO- Y is -NH- or -O- R, means hydrogen, a halogen atom, a cyano, nitro,

I C,-C.,-alkyl, trifluoromethyl, carboxyl, carboxy- R1 Ra in which R, means hydrogen, a nitro, carboxyl or carboxamide group; R stands for hydrogen or a methylsulphonyl group;

and R denotes a carboxyl, carboxamide or sulphonamide group,

with the proviso. that at least one of the radicals R,

and R is a carboxamide group. 9. Process according to claim 1 wherein said anthraquinone dyestuffs of the formula in which A denotes an anthraquinone radical which may be substituted by halogen atoms, hydroxy, nitro, amino and/or cycloalkylamino groups;

D is a carboxamide group; X denotes a single C-C bond or a grouping -NH-, -O-,

-S-, 80,-, or -SO,,-; 40 Y means a single C-C bond, an arylene, C,-C

alkylene, C,-C,,-alkylene-oxy-methylene, C,-C,,- alkylene-oxy-carbonyl-alkylene, C,-C,,-carbonylalkylene, C,-C.,-carbonyl-alkenylene or aryleneoxy-methylene radical; and n is a number from 1 to 4. 10. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula in which A denotes an anthraquinone radical which may be substituted by halogen atoms, hydroxy, nitro and- /or amino groups;

D is a carboxamide group;

Y means a C,-C.,-alkylene, C, -C,,-alkylene-oxy-carbonyl-alkylene, C,-C,,-carbonyl-alkylene or C,-C,,-carbonyl-alkenylene group; and

n is a number from 1 to 4.

11. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula in which D is a carboxamide group; R denotes a hydroxy or amino group; X stands for -O-, -S-, -SO or -SO;,-; Y means a C -C -alkylene, C -C -alkylene-oxymethylene radical, the groupings or a phenylene radical; and

Z means hydrogenor one Z means a hydroxy group and the other Z means an amino group. 13. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula in which D means a carboxamide group;

R is hydrogen or a carboxamide group; and

R is hydrogen, a hydroxy or amino group.

14. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula D l l HzN H in which D stands for a carboxamide group.

15. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a 1.9- isothiazole-anthrone dyestuff of the fomiula in which D is a carboxamide group.

16. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a dyestuff of the formula in which X and Y, independently of one another, stand for -S- A denotes a C,-C -alkylene radical, and

D means a carboxamide group.

17. Process according to claim 1 wherein said carboxamide group-containing dyestuff is a N-methylanthrapyridone dyestuff of the formula in which D stands for a carboxamide group.

18. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a phthaloylacridone dyestuff of the formula in which A denotes a c -C -alkylene radical; and

D means a carboxamide group.

19. Process according to claim 1 wherein said disperse dyestuff is a naphthoylene-benzimidazole dyestuff of the formula in which D denotes a carboxamide group.

20. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a naphthoylene-benzimidazole dyestuff of the formula in which D and D denote carboxamide groups.

21. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff, quinophthalone dyestuff of the formula 0 R1 oH/ll R4 R1 =CH H D Ra 25. The process of claim 1 wherein said dyebath contains up to 1 percent by weight of water based on the weight of the aliphatic halogenated hydrocarbon.

26. The process of claim 1 wherein said dyebath contains 0.05 to 2 percent by weight of non-ionic dyeing auxiliary based on the weight of said aliphatic haloge- PATENT NO. DATED UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 1 February 19, 1974 INVENTOR(S) Rutger Neeff and Dietmar Kalz Page 'I It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

.COLUMN LINE 1st formula last formula line 43 to the end top of page through line ERROR should read "CO-N should read Delete this portion'.

Delete this portion.

should read Page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,792,971

DATED February 19, 1974 INVENTOR(S) Rutger Neeff and Dietmar Kalz It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

H should read 15 Ex. 15 "2-aminot-nitro-" should read 2-amino5nitro l6 Ex. 35 "an ilido-gluraric acid" should read anilido-glutaric acid 17 Ex. 42 "Venzoic acid amide" should read benzoic acid amide 22 Ex. 147 "4- (4-carboyxphenylamino) should read 4-(4-carboxyphenylamino) Page 5 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,792,971

DATED February 19, 1974 v Rutger Neeff and Dietmar Kalz It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR 24 39 & 4o.

25 44 "hdyrogen" should read hydrogen 47 "hdyrogen" should read hydrogen 28 & 29 Dehze "anthraquinone dyestuffs of the formula" and insert carboxamide group-containing disperse'dyestuff is an anthraquinone dyestuff of the formula r 29 32 After the word "dyestuff" remove the comma and insert is a After line 16 insert R means hydrogen, a C C -alkyl, a C -C alkoxy group;

Signed and Scaled this sixteenth D a 0f December 19 [SEAL] Attest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner of Parents and Trademarks 

2. The process of claim 1 in which said organic solvent consists of tetrachloroethylene.
 3. Process according to claim 1, wherein said carboxamide group-containing disperse dyestuff is a monoazo dyestuff of the formula
 4. Process according to claim 1, wherein said carboxamide group-containing disperse dyestuff is a monoazo dyestuffs of the formula
 5. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a monoazo dyestuff of the formula
 6. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a disazo dyestuff of the formula
 7. Process acccording to claim 1 wherein said carboxamide group-containing disperse dyestuff is a nitro dyestuff of the formula
 8. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a nitro dyestuff of the formula
 9. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is an anthraquinone dyestuffs of the formula (A)-(X-Y-D)n in which A denotes an anthraquinone radical which may be substituted by halogen atoms, hydroxy, nitro, amino and/or cycloalkylamino groups; D is a carboxamide group; X denotes a single C-C bond or a grouping -NH-, -O-, -S-, -SO2-, or -SO3-; Y means a single C-C bond, an arylene, C1-C4-alkylene, C1-C4-alkylene-oxy-methylene, C1-C4-alkylene-oxy-carbonyl-alkylene, C1-C4-carbonyl-alkylene, C1-C4-carbonyl-alkenylene or arylene-oxy-methylene radical; and n is a number from 1 to
 4. 10. Process according to claim 1 wHerein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula (A)-(NH-Y-D)n in which A denotes an anthraquinone radical which may be substituted by halogen atoms, hydroxy, nitro and/or amino groups; D is a carboxamide group; Y means a C1-C4-alkylene, C1-C4-alkylene-oxy-carbonyl-alkylene, C1-C4-carbonyl-alkylene or C1-C4-carbonyl-alkenylene group; and n is a number from 1 to
 4. 11. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula
 12. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula
 13. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula
 14. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a anthraquinone dyestuff of the formula
 15. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a 1,9-isothiazole-anthrone dyestuff of the formula
 16. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a dyestuff of the formula
 17. Process according to claim 1 wherein said carboxamide group-containing dyestuff is a N-methyl-anthrapyridone dyestuff of the formula
 18. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a phthaloylacridone dyestuff of the formula
 19. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a naphthoylene-benzimidazole dyestuff of the formula
 20. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff is a naphthoylene-benzimidazole dyestuff of the formula
 21. Process according to claim 1 wherein said carboxamide group-containing disperse dyestuff, quinophthalone dyestuff of the formula
 22. The process of claim 1 whereIn said synthetic fiber material is polyester, polyamide, cellulose 2 1/2 acetate, cellulose triacetate, polyacrylonitrile or polyurethane.
 23. The process of claim 1 wherein said synthetic fiber material is polyester.
 24. The process of claim 1 wherein said dyestuff is an azo dyestuff.
 25. The process of claim 1 wherein said dyebath contains up to 1 percent by weight of water based on the weight of the aliphatic halogenated hydrocarbon.
 26. The process of claim 1 wherein said dyebath contains 0.05 to 2 percent by weight of non-ionic dyeing auxiliary based on the weight of said aliphatic halogenated hydrocarbon. 